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Formation of Tri‐ and Tetranuclear Titanacycles through Decamethyltitanocene‐Mediated Intermolecular C–C Coupling of Dinitriles
Author(s) -
Becker Lisanne,
Arndt Perdita,
Spannenberg Anke,
Jiao Haijun,
Rosenthal Uwe
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201500109
Subject(s) - nitrile , protonation , chemistry , intermolecular force , ring (chemistry) , alkyl , catalysis , polymerization , crystallography , medicinal chemistry , polymer chemistry , molecule , stereochemistry , organic chemistry , ion , polymer
The reactions of [Cp* 2 Ti(η 2 ‐Me 3 SiC 2 SiMe 3 )] (Cp*=η 5 ‐pentamethylcyclopentadienyl) with various dicyano compounds were investigated. Nitrile–nitrile CC couplings result in multinuclear complexes owing to the bifunctionality of the substrates. Applying 1,3‐ or 1,4‐dicyanobenzene led to tri‐ and tetranuclear complexes of the rare 1‐metalla‐2,5‐diaza‐cyclopenta‐2,4‐dienes. These are potential catalysts and were tested in the ring‐opening polymerization of ε‐caprolactone. The reaction with adiponitrile as alkyl dinitrile afforded a trinuclear 1‐metalla‐2,5‐diaza‐cyclopent‐3‐ene through additional protonation of the nitrogen atoms. The structure and bonding of the products were investigated by X‐ray crystallography and DFT analysis to understand the molecular organization in the macrocycles.